Anion Exchange in Semiconductor Magic-Size Clusters.

Ion exchange is an effective postsynthesis strategy for the design of colloidal nanomaterials with unique structures and properties. In contrast to the rapid development of cation exchange (CE), the study of anion exchange is still in its infancy and requires an in-depth understanding. Magic-size clusters (MSCs) are important reaction intermediates in quantum dot (QD) synthesis, and studying the ion exchange processes can provide valuable insights into the transformations of QDs. Here, we achieved anion exchange in Cd-based MSCs and elucidated the reaction pathways. We demonstrated that the anion exchange was a stepwise intermolecular transition mediated by covalent inorganic complexes (CICs). We proposed that this transition involved three essential steps: the disassembly of CdE1-MSCs into CdE1-CICs (step 1), an anion exchange reaction from CdE1-CICs to CdE2-CICs (step 2), and assembly of CdE2-CICs to CdE2-MSCs (step 3). Step 3 was the rate-determining step and followed first-order reaction kinetics (kobs = 0.01 min-1; from CdSe-MSCs to CdS-MSCs). Further studies revealed that the activity of foreign anions only affected the reaction kinetics without altering the reaction pathway. The present study provides a deeper insight into the anion exchange mechanisms of MSCs and will further shed light on the synthesis of QDs.

Ultrasensitive electrochemiluminescence biosensor based on dual quenching effects of silver nanoclusters and multiple cycling amplification for detection of ATP.

In this work, an electrochemiluminescence (ECL) biosensor based on dual ECL quenching effects of silver nanoclusters (Ag NCs) and multiple cycling amplification was designed to achieve ultrasensitive detection of ATP. The specific recognition of target ATP to aptamer initiated multiple cycling amplification, and a small amount of target was converted into a large number of DNA product chains (S1) by amplification. After S1 opened hairpin DNA 2 (HP2), Ag NCs approached the surface of CdS quantum dots (QDs) modified-electrode by complementary DNA, resulting in a significant decrease of ECL intensity from CdS QDs. The quenching principle is as follows. Firstly, the absorption spectrum of Ag NCs overlaps well with the ECL emission spectrum of CdS QDs, leading to effective ECL resonance energy transfer (ECL-RET); Secondly, Ag NCs could catalyze electrochemical reduction of K2S2O8, leading to consumption of ECL co-reactant and reducing ECL of QDs. The double-ECL quenching achieved ultrasensitive biosensing detection of ATP with a wide range from 1 aM to 1 pM. This present work reported new principle of double-quenching QDs ECL by Ag NCs, and developed a novel ECL biosensor by combining with multiple cycle amplification technique, which has great contribution to the development of QDs ECL and biosensing applications.

Covalent inorganic complexes enabled zinc blende to wurtzite phase changes in CdSe nanoplatelets.

Phase changes in colloidal semiconductor nanocrystals (NCs) are essential in material design and device applications. However, the transition pathways have yet to be sufficiently studied, and a better understanding of the underlying mechanisms is needed. In this work, a complete ligand-assisted phase transition from zinc blende (ZB) to wurtzite (WZ) is observed in CdSe nanoplatelets (NPLs). By monitoring with in situ absorption spectra along with electrospray ionization mass spectrometry (ESI-MS), we demonstrated that the transition process is a ligand-assisted covalent inorganic complex (CIC)-mediated phase transition pathway, which involves three steps, ligand exchange on ZB CdSe NPLs (Step 1), dissolution of NPLs to form CICs (Step 2), and conversion of CdSe-CIC assemblies to WZ CdSe NPLs (Step 3). In particular, CICs can be directly anisotropically grown to WZ CdSe NPL without other intermediates, following pseudo-first-order kinetics (kobs = 9.17 × 10-5 s-1). Furthermore, we demonstrated that CICs are also present and play an essential role in the phase transition of ZnS NPLs from WZ to ZB structure. This study proposes a new crystal transformation pathway and elucidates a general phase-transition mechanism, facilitating precise functional nanomaterial design.

Surface passivation of intensely luminescent all-inorganic nanocrystals and their direct optical patterning.

All-inorganic nanocrystals (NCs) are of great importance in a range of electronic devices. However, current all-inorganic NCs suffer from limitations in their optical properties, such as low fluorescence efficiencies. Here, we develop a general surface treatment strategy to obtain intensely luminescent all-inorganic NCs (ILANs) by using designed metal salts with noncoordinating anions that play a dual role in the surface treatment process: (i) removing the original organic ligands and (ii) binding to unpassivated Lewis basic sites to preserve the photoluminescent (PL) properties of the NCs. The absolute photoluminescence quantum yields (PLQYs) of red-emitting CdSe/ZnS NCs, green-emitting CdSe/CdZnSeS/ZnS NCs and blue-emitting CdZnS/ZnS NCs in polar solvents are 97%, 80% and 72%, respectively. Further study reveals that the passivated Lewis basic sites of ILANs by metal cations boost the efficiency of radiative recombination of electron-hole pairs. While the passivation of Lewis basic sites leads to a high PLQY of ILANs, the exposed Lewis acidic sites provide the possibility for in situ tuning of the functions of NCs, creating opportunities for direct optical patterning of functional NCs with high resolution.

Designing inorganically functionalized magic-size II-VI clusters and unraveling their surface states.

Surface engineering is a critical step in the functionalization of nanomaterials to improve their optical and electrochemical properties. However, this process remains a challenge in II-VI magic-size clusters (MSCs) due to their high sensitivity to the environment. Herein, we developed a general surface modification strategy to design all-inorganic MSCs by using certain metal salts (cation = Zn2+, In3+; Anion = Cl-, NO3 -, OTf-) and stabilized (CdS)34, (CdSe)34 and (ZnSe)34 MSCs in polar solvents. We further investigated the surface states of II-VI MSCs using electrochemiluminescence (ECL). The mechanism study revealed that the ECL emission was attributed to . Two ECL emissions at 556 nm and 530 nm demonstrated two surface passivation modes on (CdS)34 MSCs, which can be tuned by the surface ligands. The achievement of surface engineering opens a new design space for functional MSC compounds.

Progress in electrochemiluminescence of nanoclusters: how to improve the quantum yield of nanoclusters.

Luminescent nanoclusters (NCs), with their easy preparation, ultrafine size, low toxicity, and excellent photostability have recently emerged as novel electrochemiluminescence (ECL) emitters. However, relatively low quantum yield (QY) in both aqueous and organic media has impeded their application in ECL emitter evolution. In this mini-review, we discuss the recent development of NCs in ECL with particular focus on their optical properties. We first classify the NCs according to composition and structure, and then summarize four aspects that affect QY, including environment effects, construction, valence state effects and aggregation-induced ECL. The ECL mechanisms based on NCs are elucidated as well. Finally, we briefly discuss the potential applications of NCs in tumor markers test, immunoassay and serum test. This review aims to provide a comprehensive summary of the progress of NCs in ECL, which will motivate researchers to develop NC chemistry and explore their future applications in ECL.

3D DNA nanosphere-based photoelectrochemical biosensor combined with multiple enzyme-free amplification for ultrasensitive detection of cancer biomarkers.

In this work, a new 3D DNA nanosphere was ingeniously designed and fabricated, which was used to combine with multiple enzyme-free amplification strategy to develop a photoelectrochemical (PEC) biosensing platform for ultrasensitive detection of carcinoembryonic antigen (CEA). The 3D DNA nanostructure was self-assembled by base complementary pairing in a few minutes and rolling circle amplification (RCA) reaction. The intense photocurrent derived from Au NPs/ZnSe QDs can be effectively decreased by 3D DNA nanospheres assembled on the electrode, making photoelectric signal present "off" state. The specific binding of target CEA with its hairpin (HP1) aptamer opens HP1 structure, which initiated multiple enzyme-free strand displacement amplification (SDA) reaction and generated a large number of single strands DNA S1. Then S1 competitively binds to capture DNA on the electrode to release 3D DNA nanospheres, thus the photocurrent signal became "on" state for achieving amplified assay of target CEA. The proposed PEC biosensor exhibits excellent performance with a wide linear range of 1.0 fg/mL to 10 ng/mL and a low detection limit of 0.12 fg/mL for CEA, which was successfully applied for the assay of real serum samples with good precision. The reported strategy opens a new simple way for PEC biosensor using DNA nanostructure, showing huge potential in clinical application research.

Versatile Electrochemiluminescence and Photoelectrochemical Detection of Glutathione Using Mn2+ Substitute Target by DNA-Walker-Induced Allosteric Switch and Signal Amplification.

Glutathione (GSH) serves vital functions in biological systems and associates with various human diseases. In this work, a versatile electrochemiluminence (ECL) and a photoelectrochemical (PEC) "signal on" biosensing platform were developed for a sensitive assay of GSH by a Mn2+-powered DNAzyme amplification strategy combined with DNA-walker-triggered allosteric conversion. First, MnO2 nanosheets were reduced to Mn2+ by GSH; then, Mn2+ as a substitute target triggered DNAzyme-assisted cleavage-cycling amplification to generate numerous DNA output (s3). Meanwhile, the DNA molecular machine was introduced to bridge signal probes for versatile biosensing, which included hairpin DNA as a track and an arm as a walker. The presence of DNA output (s3) activated the swing arm to hybridize with hairpin DNA and then cut it by Nt.BbvCI, which initiated autonomous walking of the arm for forming a large number of streptavidin (SA) aptamers. Thus, a large number of CdS:Mn-SA tags as versatile signal probes was linked to the electrode by specific SA-aptamer binding, generating highly enhanced ECL and PEC signals for sensitive detection of the target. The present biosensing system take advantage of metal ion-based DNAzyme amplification, a DNA walker machine, multi-signals of QDs, and specificity of aptamers, which can provide a universal and efficient biosensing method for detecting various targets. The designed strategy demonstrated good performance for a GSH assay in human serum samples, showing more promising applications than other reported methods.

Versatile "on-off" biosensing of thrombin and miRNA based on Ag(i) ion-enhanced or Ag nanocluster-quenched electrochemiluminescence coupled with hybridization chain reaction amplification.

A novel biosensing platform based on the Ag(i) ion-enhanced or Ag nanocluster (NC)-quenched electrochemiluminescence (ECL) of CdSe quantum dots (QDs) was designed for versatile "on-off" assays of thrombin (TB) and miRNA, in which bipedal molecular machine (BMM)-triggered surface programmatic chain reaction (SPCR) coupled with mesoporous silica nanoparticle (MSN) multiple amplification is used to introduce plentiful QDs and Ag+ ions to significantly improve the ECL signal.

Versatile fluorescence detection of microRNA based on novel DNA hydrogel-amplified signal probes coupled with DNA walker amplification.

A novel DNA hydrogel-amplified versatile fluorescence platform combined with hybridization chain reaction (HCR) and DNA walking multiple amplification was developed for ultrasensitive detection of miRNA. The DNA hydrogel was loaded with large amounts of SYBR Green (SG) I dyes or CdTe quantum dots (QDs) to assemble versatile signal probes.

Versatile Electrochemiluminescence and Electrochemical "On-Off" Assays of Methyltransferases and Aflatoxin B1 Based on a Novel Multifunctional DNA Nanotube.

Herein, a new multifunctional DNA nanotube (DNANT) was self-assembled and used to load Ru(phen)32+ and methylene blue (MB) as amplified signal probes for versatile electrochemiluminescence (ECL) and electrochemical (EC) "on-off" assays of Dam methylase (MTase) and aflatoxin B1 (AFB1). The DNA nanotube as a carrier could immobilize numerous MB or Ru(phen)32+ species in the double-stranded DNA (dsDNA) to significantly amplify signals, which enabled highly sensitive ECL and electrochemical detection of dual targets. The target Dam MTase first catalyzed the methylation of hairpin DNA (H1), and then the methylated DNA was cleaved by endonuclease DpnI to expose a single-strand DNA. After the Ru(phen)32+-DNANT or MB-DNANT signal probes were assembled to the electrode by hybridization, remarkable "signal on" states for amplified ECL or EC assays of MTase were obtained. Furthermore, in the presence of the target AFB1, the structure of DNANTs collapsed due to the specific binding of AFB1 to aptamer S2 in NTs, which led to the release of signal probes (Ru(phen)32+ or MB) from the electrode to achieve "signal off" state for dual detection of AFB1. Taking advantage of the multifunctional DNANT amplification signal probes, the versatile biosensors showed good analytical performance with very wide linear ranges (0.001-100 U mL-1 and 0.0001-100 ng mL-1 for MTase and AFB1 assay by DPV) and lower detection limits (2.1 × 10-4 U mL-1 and 0.018 pg mL-1 for MTase and AFB1 by DPV). This is the first time that ECL and EC "on-off" methods have been achieved separately for dual target assays, which opens a new avenue of DNANT-based signal amplification strategyies for the versatile design of biosensors in various biological detections.

Multifunctional DNA nanocage with CdTe quantum dots for fluorescence detection of human 8-oxoG DNA glycosylase 1 and doxorubicin delivery to cancer cells.

A multifunctional DNA nanocage containing CdTe quantum dots (QDs) was prepared. It was applied to the fluorometric detection of human 8-oxoG DNA glycosylase 1 (hOGG1) by exonuclease-assisted cycling amplification technique. When loaded with the cancer drug doxorubicin (Dox), the nanocage is also a versatile probe for fluorescence imaging of cancer cells, and drug delivery to them. The presence of hOGG1 leads to the division of DNA HP1 (containing 8-oxo-dG) and formation of DNA fragments 1 and 2. Then, HP2 is added to hybridize with DNA 1 and produced lots of trigger DNA (containing nucleolin aptamer) by Exo III-aided cycling amplification. The DNA nanocage was fabricated by linking the trigger DNA to multiple specific DNA strands, and the fluorescent CdTe QDs were further conjugated to the DNA nanocage for sensitive detection of hOGG1 activity. After Dox is incorporated into the DNA nanocage, the fluorescence of Dox is turned off. Once the DNA nanocage enters the MCF-7 cells, the Dox is released and its fluorescence (measured at excitation/emission wavelengths of 480/560 nm) is turned on. The DNA nanocage containing fluorescent QDs and Dox was successfully applied to the fluorometric detection of hOGG1, fluorescence imaging, and therapy of cancer cells, which has great promise in clinical application and treatment of cancer. Graphical abstract A multifunctional DNA nanocage containing CdTe quantum dots and acting as a signalling probe was prepared. It was applied to fluorometric determination of human 8-oxoG DNA glycosylase 1 using cycling amplification technique. It also enables drug delivery to cancer cells if loaded with doxorubicin.

Amplified electrochemiluminescence detection of CEA based on magnetic Fe3O4@Au nanoparticles-assembled Ru@SiO2 nanocomposites combined with multiple cycling amplification strategy.

In this work, we designed a new strategy for ultrasensitive detection of CEA based on efficient electrochemiluminescence (ECL) quenching of Ru(bpy)32+-doped SiO2 nanocomposite by ferrocene using target recycling amplification technique. A large number of Ru@SiO2 ECL signal probe were firstly assembled on the novel magnetic core-shell Fe3O4@Au nanoparticles (NPs), then the ferrocene-labeled ECL quenching probe (Fc-probe) was linked to the magnetic NPs. Finally, numerous DNA1 sequences were produced by target CEA-triggered multiple recycling amplification and displaced the Fc-probe on the magnetic NPs, leading to significantly enhanced ECL signal for CEA detection. Because of the designed cascade signal amplification strategy, the newly developed method achieved a wide linear range of 10 fg/mL to 10 ng/mL with a low detection limit of  3.5 fg/mL. Furthermore, taking advantages of the magnetic Fe3O4@Au NPs for carring abundant signal probes, sensing target and ECL detection, the developed ECL strategy is convenient, rapid and displayed high sensitivity for CEA detection, which has great potential for analyzing the clinical samples in practical disease diagnosis applications.

Amplified electrochemiluminescence detection of DNA based on novel quantum dots signal probe by multiple cycling amplification strategy.

In the present work, we designed a unique enzyme-aided multiple amplification strategy for sensitive electrochemiluminescence (ECL) detection of DNA by using the amplified gold nanoparticles (GNPS)-polyamidoamine (PAMAM)-CdSe quantum dots (QDs) signal probe. Firstly, the novel GNPS-PAMAM dendrimers nanostructure with good biocompatibility and electroconductibility contains many amino groups, which can load a large number of CdSe QDs to develop amplified ECL signal probe. Then, the presence of target DNA activated the enzyme-assisted polymerization strand-displacement cycling reaction, and a large number of the hairpin template was opened. Subsequently, the opened stem further interacted with the capture hairpin (HP) DNA on the electrode, and the GNPS-PAMAM-CdSe signal probe hybridized with the exposed stem of the HP to trigger the second new polymerization reaction. Meanwhile, the first cycle was generating abundant DNA triggers which could directly open the template. As a result of the cascade amplification technique, a large number of CdSe QDs signal probe could be assembled on the electrode, generating much amplified ECL signal for sensitive detection of target DNA. Thus, this novel QDs-based amplified ECL strategy holds great promise for DNA detection and can be further exploited for sensing applications in clinical diagnostics.

Two new tetracyclic triterpenoids from the barks of Melia azedarach.

Two new tetracyclic triterpenoids, together with 21 known compounds, were isolated from the barks of Melia azedarach. The structures of new compounds were elucidated by the means of HRESIMS, 1D NMR, 2D NMR, and X-ray crystallography analysis.

Crystal structure of 16-hy-droxy-4,4,10,13,14-penta-methyl-17-(6-methyl-hept-5-en-2-yl)-4,5,6,9,10,11,12,13,14,15,16,17-dodeca-hydro-1H-cyclo-penta-[a]phenanthren-3(2H)-one.

The title compound, C30H48O2, contains a fused four-ring triterpenoid system. In the mol-ecule, the two cyclo-hexane rings adopt a chair conformation and a twist boat conformation, respectively, the central cyclo-hexene ring adopts a half-chair conformation whereas the five membered ring adopts an envelope conformation. In the crystal, O-H⋯O hydrogen bonds between the hy-droxy and carbonyl groups of adjacent mol-ecules link the mol-ecules into supra-molecular chains propagating along the b-axis direction.